RESUMEN
The tandem CO2 hydrogenation to hydrocarbons over mixed metal oxide/zeolite catalysts (OXZEO) is an efficient way of producing value-added hydrocarbons (platform chemicals and fuels) directly from CO2via methanol intermediate in a single reactor. In this contribution, two MAPO-18 zeotypes (M = Mg, Si) were tested and their performance was compared under methanol-to-olefins (MTO) conditions (350 °C, PCH3OH = 0.04 bar, 6.5 gCH3OH h-1 g-1), methanol/CO/H2 cofeed conditions (350 °C, PCH3OH/PCO/PH2 = 1:7.3:21.7 bar, 2.5 gCH3OH h-1 g-1), and tandem CO2 hydrogenation-to-olefin conditions (350 °C, PCO2/PH2 = 7.5:22.5 bar, 1.4-12.0 gMAPO-18 h molCO2-1). In the latter case, the zeotypes were mixed with a fixed amount of ZnO:ZrO2 catalyst, well-known for the conversion of CO2/H2 to methanol. Focus was set on the methanol conversion activity, product selectivity, and performance stability with time-on-stream. In situ and ex situ Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), solid-state nuclear magnetic resonance (NMR), sorption experiments, and ab initio molecular dynamics (AIMD) calculations were performed to correlate material performance with material characteristics. The catalytic tests demonstrated the better performance of MgAPO-18 versus SAPO-18 at MTO conditions, the much superior performance of MgAPO-18 under methanol/CO/H2 cofeeds, and yet the increasingly similar performance of the two materials under tandem conditions upon increasing the zeotype-to-oxide ratio in the tandem catalyst bed. In situ FT-IR measurements coupled with AIMD calculations revealed differences in the MTO initiation mechanism between the two materials. SAPO-18 promoted initial CO2 formation, indicative of a formaldehyde-based decarboxylation mechanism, while CO and ketene were the main constituents of the initiation pool in MgAPO-18, suggesting a decarbonylation mechanism. Under tandem CO2 hydrogenation conditions, the presence of high water concentrations and low methanol partial pressure in the reaction medium led to lower, and increasingly similar, methanol turnover frequencies for the zeotypes. Despite both MAPO-18 zeotypes showing signs of activity loss upon storage due to the interaction of the sites with ambient humidity, they presented a remarkable stability after reaching steady state under tandem reaction conditions and after steaming and regeneration cycles at high temperatures. Water adsorption experiments at room temperature confirmed this observation. The faster activity loss observed in the Mg version is assigned to its harder Mg2+-ion character and the higher concentration of CHA defects in the AEI structure, identified by solid-state NMR and XRD. The low stability of a MgAPO-34 zeotype (CHA structure) upon storage corroborated the relationship between CHA defects and instability.
RESUMEN
Metal-organic frameworks (MOFs) are porous hybrid materials with countless potential applications. Most of these rely on their porous structure, tunable composition, and the possibility of incorporating and expanding their functions. Although functionalization of the inner surface of MOF crystals has received considerable attention in recent years, methods to functionalize selectively the outer crystal surface of MOFs are developed to a lesser extent, despite their importance. This article summarizes different types of post-synthetic modifications and possible applications of modified materials such as: catalysis, adsorption, drug delivery, mixed matrix membranes, and stabilization of porous liquids.
RESUMEN
Metal-organic frameworks (MOF) are a new type of porous materials that have great potential for adsorption of voltaic organic compounds (VOCs). These types of materials composed of metal ions and organic ligands are easy to synthesize, have high surface areas, their surface chemistry can be adjusted to the desired application, and they can also have good chemical and thermal stability. Therefore, this work focuses on the synthesis of a highly hydrophobic MOF material called CIM-80, a porous material that is made up of the Al3+ cation and the mesaconate linker. This MOF has a B.E.T. of approximately 800 m2/g and has potential applications for the adsorption of hydrophobic organic compounds. However, its synthesis is expensive and very dirty. Therefore, we have studied the synthesis conditions necessary to achieve high synthesis yields (85%) and materials with high crystallinity and accessible porosity. To achieve these results, we have used urea as a mild deprotonation reagent and modulator as an alternative to NaOH, which is traditionally used for the synthesis of this MOF. Once the synthesis of this material was controlled, its adsorption/desorption behavior of water and organic compounds such as toluene, cyclohexane and m-xylene was studied by means of vapor adsorption isotherms. The results show the hydrophobic character of the material and the greater affinity the material has toward aliphatic compounds than toward aromatic ones, with toluene being the most adsorbed compound, followed by cyclohexane and m-xylene.
